Resonance Raman Characterization of Tetracene Monomer and Nanocrystals: Excited State Lattice Distortions With Implications For Efficient Singlet Fission.

The characterization of specific phonon modes and exciton states that lead to efficient singlet fission (SF) may be instrumental in the design of the next generation of high-efficiency photovoltaic devices. To this end, we analyze the absolute resonance Raman (RR) cross sections for tetracene (Tc) both as a monomer in solution and as a crystalline solid in an aqueous suspension of nanocrystals. For both systems, a time-dependent wavepacket model is developed that is consistent with the absolute RR cross sections, the magnitude of the absorption cross sections, and the vibronic line shapes of the fluorescence. In the monomer, the intramolecular reorganization energy is between 1500 and 1800 cm-1 and the solvent reorganization energy is 70 cm-1. In nanocrystals, the total reorganization is diminished to less than 600 cm-1. The lowest energy exciton has an estimated intramolecular reorganization energy between 300 and 500 cm-1 while intermolecular librational phonons have a reorganization energy of about 130 cm-1. The diminished reorganization energy of the nanocrystal is interpreted in the context of the delocalization of the band-edge exciton onto about ∼7 molecules. When electron and electron-hole correlations are included within many-body perturbation theory, the polarized absorption spectra of crystalline Tc are calculated and found to be in agreement with experiment. The low-lying exciton states and optically active phonons that contribute to the polarized crystal absorption are identified. The likely role of coherent exciton phonon evolution in the SF process is discussed.

Difference Bands in Time-Resolved Femtosecond Stimulated Raman Spectra of Photoexcited Intermolecular Electron Transfer from Chloronaphthalene to Tetracyanoethylene.

The time-resolved femtosecond stimulated Raman spectra (FSRS) of a charge transfer (CT) excited noncovalent complex tetracyanoethylene:1-chloronaphthalene (TCNE:ClN) in dichloromethane (DCM) is reported with 40 fs time resolution. In the frequency domain, five FSRS peaks are observed with frequencies of 534, 858, 1069, 1392, and 1926 cm-1. The most intense peaks at 534 and 1392 cm-1 correspond to fundamentals while the features at 858, 1069, and 1926 cm-1 are attributed to a difference frequency, an overtone and a combination frequency of the fundamentals, respectively. The frequency of the 1392 cm-1 fundamental corresponding to the central C═C stretch of TCNE•- is red-shifted from the frequency of the steady state radical due to the close proximity and electron affinity of the countercation. The observation of a FSRS band at a difference frequency is analyzed. This analysis lends evidence for alternative nonlinear pathways of inverse Raman gain scattering (IRGS) or vertical-FSRS (VFSRS) which may contribute to the time-evolving FSRS spectrum on-resonance. Impulsive stimulated Raman measurements of the complex show coherent oscillations of the stimulated emission with frequencies of 153, 278, and 534 cm-1. The 278 cm-1 mode corresponds to Cl bending of the dichloromethane solvent. The center frequency of the 278 cm-1 mode is modulated by a frequency of ∼30 cm-1 which is attributed to the effect of librational motion of the dichloromethane solvent as it reorganizes around the nascent contact ion pair. The 153 ± 15 cm-1 mode corresponds to an out-of-plane bending motion of TCNE. This motion modulates the intermolecular separation of the contact ion pair and thereby the overlap of the frontier orbitals which is crucial for rapid charge recombination in 5.9 ± 0.2 ps. High time-frequency resolution vibrational spectra provide unique molecular details regarding charge localization and recombination.

Supramolecular Ga4L6(12-) Cage Photosensitizes 1,3-Rearrangement of Encapsulated Guest via Photoinduced Electron Transfer.

The K12Ga4L6 supramolecular cage is photoactive and enables an unprecedented photoreaction not observed in bulk solution. Ga4L6(12-) cages photosensitize the 1,3-rearrangement of encapsulated cinnamylammonium cation guests from the linear isomer to the higher energy branched isomer when irradiated with UVA light. The rearrangement requires light and guest encapsulation to occur. The Ga4L6(12-) cage-mediated reaction mechanism was investigated by UV/vis absorption, fluorescence, ultrafast transient absorption, and electrochemical experiments. The results support a photoinduced electron transfer mechanism for the 1,3-rearrangement, in which the Ga4L6(12-) cage absorbs photons and transfers an electron to the encapsulated cinnamylammonium ion, which undergoes C-N bond cleavage, followed by back electron transfer to the cage and recombination of the guest fragments to form the higher energy isomer.

Characterization of a conical intersection in a charge-transfer dimer with two-dimensional time-resolved stimulated Raman spectroscopy.

Photochemical reactions are mediated by conical intersections (CI), which are difficult to directly probe and characterize. To gain insight into CIs, two-dimensional femtosecond stimulated Raman spectroscopy (2D-FSRS) is used to examine a model excited-state charge-transfer (CT) complex consisting of an electron donor, tetramethylbenzene (TMB), and an acceptor, tetracyanoquinodimethane (TCNQ). Following impulsive excitation, the excited-state transient absorption reveals large-amplitude excited-state wave packet motion along low-frequency modes, in particular TCNQ's totally symmetric 323 cm(-1) CCN bend, which persist for ∼5 ps. These low-frequency coherences modulate the intensity and peak frequencies of the excited-state FSRS vibrational spectra. In particular, large-magnitude oscillations at 323 cm(-1) are observed in the peak frequency (Δω = 2 cm(-1)) and intensity (ΔOD = 1.5 mOD) of the nontotally symmetric 1271 cm(-1) C═C rocking mode. The magnitude of these oscillations is analyzed to determine the first-order anharmonic coupling between the high- and low-frequency degrees of freedom in the excited state. The anharmonic coupling between the totally symmetric 323 cm(-1) and the nontotally symmetric 1271 cm(-1) modes is estimated to be in excess of 50 cm(-1), strongly suggesting that they are the tuning and coupling modes, respectively, for the CI that connects the CT excited state to the neutral ground state and controls charge recombination internal conversion.

Picosecond carrier dynamics in InAs and GaAs revealed by ultrafast electron microscopy.

Understanding the limits of spatiotemporal carrier dynamics, especially in III-V semiconductors, is key to designing ultrafast and ultrasmall optoelectronic components. However, identifying such limits and the properties controlling them has been elusive. Here, using scanning ultrafast electron microscopy, in bulk n-GaAs and p-InAs, we simultaneously measure picosecond carrier dynamics along with three related quantities: subsurface band bending, above-surface vacuum potentials, and surface trap densities. We make two unexpected observations. First, we uncover a negative-time contrast in secondary electrons resulting from an interplay among these quantities. Second, despite dopant concentrations and surface state densities differing by many orders of magnitude between the two materials, their carrier dynamics, measured by photoexcited band bending and filling of surface states, occur at a seemingly common timescale of about 100 ps. This observation may indicate fundamental kinetic limits tied to a multitude of material and surface properties of optoelectronic III-V semiconductors and highlights the need for techniques that simultaneously measure electro-optical kinetic properties.

Optimally shaped narrowband picosecond pulses for femtosecond stimulated Raman spectroscopy.

A comparison between a Fabry-Pérot etalon filter and a conventional grating filter for producing the picosecond (ps) Raman pump pulses for femtosecond stimulated Raman spectroscopy (FSRS) is presented. It is shown that for pulses of equal energy the etalon filter produces Raman signals twice as large as that of the grating filter while suppressing the electronically resonant background signal. The time asymmetric profile of the etalon-generated pulse is shown to be responsible for both of these observations. A theoretical discussion is presented which quantitatively supports this hypothesis. It is concluded that etalons are the ideal method for the generation of narrowband ps pulses for FSRS because of the optical simplicity, efficiency, improved FSRS intensity and reduced backgrounds.

Low frequency resonant impulsive Raman modes reveal inversion mechanism for azobenzene.

Azobenzenes are versatile photoswitches that find application in optical memory, light-driven motors, and molecular gating. Despite many studies, the molecular details of their light induced trans to cis isomerization are still debated. To inform this discussion we probed the low frequency skeletal motions in an azobenzene derivative, 4-nitro-4'-dimethylamino-azobenzene (NDAB), with resonant impulsive stimulated Raman spectroscopy (RISRS). Four previously unobserved modes at 14, 47, 150, and 201 cm(-1) were found. Of these, the ∼50 cm(-1) inversion motion and the ∼15 cm(-1) torsional motion had particularly large intensities, suggesting that the excited state potential energy surface is steeply sloped along these coordinates in the Franck-Condon region. These data support a model in which NDAB isomerizes predominantly along a prompt inversion coordinate as well as a slower torsional motion that mitigates the phenyl-phenyl interactions on the pathway to the isomerized product.

Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite.

Hybrid organic-inorganic perovskites have attractive optoelectronic properties including exceptional solar cell performance. The improved properties of perovskites have been attributed to polaronic effects involving stabilization of localized charge character by structural deformations and polarizations. Here we examine the Pb-I structural dynamics leading to polaron formation in methylammonium lead iodide perovskite by transient absorption, time-domain Raman spectroscopy, and density functional theory. Methylammonium lead iodide perovskite exhibits excited-state coherent nuclear wave packets oscillating at ~20, ~43, and ~75 cm-1 which involve skeletal bending, in-plane bending, and c-axis stretching of the I-Pb-I bonds, respectively. The amplitudes of these wave packet motions report on the magnitude of the excited-state structural changes, in particular, the formation of a bent and elongated octahedral PbI64- geometry. We have predicted the excited-state geometry and structural changes between the neutral and polaron states using a normal-mode projection method, which supports and rationalizes the experimental results. This study reveals the polaron formation via nuclear dynamics that may be important for efficient charge separation.

Modeling of aqueous transport in rigid porous matrices near the percolation threshold.

PURPOSE: To demonstrate control of passive diffusion of small molecules through rigid ceramic matrices via manipulation of matrix porosity near the percolation threshold, and to model such control using percolation scaling relationships on both infinite and finite lattices. MATERIALS AND METHODS: Rigid alumina disks of controlled porosity were prepared using standard ceramic casting and sintering techniques. Structural void space distributions in sintered disks were measured by dimensional and volume displacement (pycnometry) methods. The impact of void space on transport was determined by tracking the diffusion of ionized benzoic acid across sintered disks mounted in Stokes diffusion cells. Critical percolation thresholds were estimated by fitting structural and transport-dependent results to percolation scaling relationships. Finite-size scaling studies were performed by adding polymer microspheres of known diameter to the disks to generate artificially large pores. RESULTS: Nonlinear least squares techniques were used to fit both structural and transport-dependent properties of rigid alumina disks to total disk porosity using percolation scaling relationships. The critical percolation threshold determined from structural properties (0.129) was lower than that determined from benzoic acid transport (0.169). The transport-derived percolation threshold exactly matched that expected for a tetrakaidecahedral (14 sided) lattice. Finite-size scaling was demonstrated through a nonzero effective volume fraction for transport at the percolation threshold. CONCLUSIONS: Manipulation of total disk porosity near the percolation threshold was shown to be a suitable means of controlling the transport rate of a model small molecule, while deliberate enlargement of individual pores was demonstrated to decrease this threshold without increasing total porosity. The lower-than-expected percolation threshold obtained from the structural model was ascribed to limitations of the measurement technique. The threshold determined from the aqueous transport model was concluded to represent the true threshold for this system.